US4143033A - Water-soluble disazo dyestuffs containing a 2-phenyl-benzimidazolyl,-benzoxazolyl or-benzthiazolyl middle component - Google Patents

Water-soluble disazo dyestuffs containing a 2-phenyl-benzimidazolyl,-benzoxazolyl or-benzthiazolyl middle component Download PDF

Info

Publication number
US4143033A
US4143033A US05/778,049 US77804977A US4143033A US 4143033 A US4143033 A US 4143033A US 77804977 A US77804977 A US 77804977A US 4143033 A US4143033 A US 4143033A
Authority
US
United States
Prior art keywords
alkyl
carbons
carbon atoms
acid
hydroxy
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US05/778,049
Other languages
English (en)
Inventor
Wolfgang Bauer
Joachim Ribka
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sanofi Aventis Deutschland GmbH
Original Assignee
Cassella AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Cassella AG filed Critical Cassella AG
Application granted granted Critical
Publication of US4143033A publication Critical patent/US4143033A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B35/00—Disazo and polyazo dyes of the type A<-D->B prepared by diazotising and coupling
    • C09B35/02—Disazo dyes
    • C09B35/039—Disazo dyes characterised by the tetrazo component
    • C09B35/34—Disazo dyes characterised by the tetrazo component the tetrazo component being heterocyclic

Definitions

  • the present invention relates to water-soluble disazo dyes.
  • X is --N--, --O-- or --S--,
  • R denoting hydrogen, alkyl having up to 4 carbons, phenyl or benzyl
  • R 1 and R 2 being identical or different, each representing alkyl having up to 4 carbons, alkyl carbonyl having 2 to 5 carbons, aryl or aroyl each having 6 to 12 carbons, hydroxyalkyl having 2 to 4 carbons or sulfoalkyl or carboxyalkyl each having up to four alkyl carbons, and one of R 1 and R 2 can be hydrogen,
  • a 1 is a radical of a hydroxy-benzene, aminobenzene, amino-hydroxy-benzene, hydroxynaphthalene, N-mono- or N,N-disubstituted aminonaphthalene, N-mono- or N,N-disubstituted amino-hydroxy-naphthalene, pyrazolone, 6-hydroxy-2-pyridone, 2,6-diaminopyridine, acetoacetic acid arylamide or dihydroxyquinoline coupling component.
  • the non-vicinal designation applied to one of the bonds means that the bond goes to a position on the benzene ring remote from the heterocyclic ring to which the benzene ring is fused.
  • the radical of the coupling component is derived from the benzene series, it is a phenyl radical which is monosubstituted or disubstituted by amino and/or hydroxyl and the amino groups can also be monosubstituted or disubstituted by alkyl radicals or monosubstituted by aryl, aroyl or alkyl carbonyl, or disubstituted by alkyl carbonyl and alkyl or aryl and alkyl, or monosubstituted or disubstituted by carboxyalkyl, sulfoalkyl or hydroxyalkyl.
  • the radical of the coupling component is derived from the naphthalene series, it is a 1-naphthyl or 2-naphthyl radical which is monosubstituted or disubstituted by a substituted amino group and/or hydroxyl group and the amino groups are mono- or disubstituted by alkyl radicals or monosubstituted by aryl, aroyl or alkyl carbonyl, or disubstituted by alkyl carbonyl and alkyl or aryl and alkyl, or monosubstituted or disubstituted by carboxyalkyl, sulfoalkyl or hydroxyalkyl.
  • the phenyl nucleus of said coupling components can also be further substituted by alkyl, alkoxy, alkylthio, cyano, nitro, sulfo, carboxyl, halogen, alkoxycarbonyl, acyl or aroyl.
  • the naphthyl nucleus of said coupling components can also be further substituted by alkyl, alkoxy, sulfo, carboxyl, halogen.
  • the alkyl, alkoxy, alkylthio and alkoxycarbonyl present in said coupling components have 1-4 C atoms, the aryl and aroyl radicals have 6-12 C atoms, the alkyl carbonyl radicals have 2-5 C atoms, the carboxyalkyl and sulfoalkyl radicals have 1-2 C atoms and the hydroxyalkyl radicals have 2 C atoms.
  • the phenyl radical is monosubstituted or disubstituted by amino and/or hydroxyl and the amino groups can carry one sulfoethyl, sulfomethyl, carboxymethyl, carboxyethyl, hydroxyethyl, acetyl, benzoyl, phenyl or tolyl substituent or one or two methyl or ethyl substituents and the phenyl radical can also be monosubstituted additionally by alkyl having 1-2 C atoms, alkoxy having 1-2 C atoms, carboxyl, sulfo, chloro or nitro.
  • a further preferred group of dyestuffs according to the invention contains an ⁇ -naphthyl or ⁇ -naphthyl radical which is monosubstituted or disubstituted by a substituted amino group and/or hydroxyl group and the amino groups carry one sulfoethyl, sulfomethyl, carboxymethyl, carboxyethyl, hydroxyethyl, acetyl, benzoyl, phenyl or tolyl substituent or one or two methyl or ethyl substituents and the naphthyl radical can also be monosubstituted additionally by sulfo, carboxyl or chlorine or disubstituted additionally by --SO 3 H.
  • R 3 is hydrogen, alkyl having up to 4 carbons, or phenyl or naphthyl both of which can be substituted by sulfo, nitro, amino, cyano, halo, alkyl having up to 4 carbons, or alkoxy having up to 4 carbons, and
  • R 4 is hydrogen, alkyl having up to 4 carbons, carboxyl, or alkoxycarbonyl having up to 5 carbons.
  • R 5 and R 7 are independently hydrogen or alkyl having up to 4 carbons
  • R 6 is hydrogen, cyano, --CONH 2 or SO 3 H
  • the radical of the coupling component is an acetoacetic acid arylamide
  • the preferred structures are ##STR6## where R 8 is phenyl or naphthyl both of which can be substituted by sulfo, carboxyl, halogen, alkyl having up to 4 carbons and alkoxy having up to four carbons.
  • the radical of a coupling component in the dyestuffs according to the invention can also be a 2,4-dihydroxy-2-quinolyl or 2,6-diamino-5-pyridyl radical.
  • the nuclei I and II of the heterocyclic middle component can be substituted by one or two identical or different substituents from the group of alkyl and/or alkoxy, each having 1 or 2 C atoms, and/or halogen.
  • Dyestuffs according to the invention in which the nuclei I and/or II are unsubstituted or are substituted by a methyl group or chlorine, are preferred.
  • Dyestuffs according to the invention, in which the heterocyclic middle component is a divalent radical of 2-phenylbenzimidazole are particularly preferred.
  • the dyes of the present invention are readily prepared by coupling a diazotized monoazo dye such as
  • y.sup. ⁇ is the anion of a mineral acid as hydrochloric or sulfuric acid, with the remaining component of the desired dye.
  • the coupling takes place in the 7-position of the coupling components VII, VIII and IX, as shown, while at acid acid pH values of 1 to 5 the coupling takes place with the N-substituted 2-amino-8-hydroxynaphthalenesulfonic acid of the formula VII in the 1-position and with the N-substituted 3-amino-8-hydroxynaphthalensulfonic acid of the formula VIII in the 4-position of the naphthalene nucleus.
  • a tetrazo compound of the formula XV ##STR12## wherein y - is the anion of a mineral acid, is coupled in any desired sequence with a key coupling component of the formula IIa or IIIa in the pH range between 0 and 14, and with the second coupling component of A and A 1 in the pH range from 7 to 14 or, of said second coupling component is a coupling component of the aniline or naphthylamine series, in the pH range from 0 to 14.
  • Either or both of the diazonium groups of the tetrazo compound XV can couple at the first coupling step so that isomeric coupling products are obtained, usually in mixtures. These isomers only differ from each other by the inversion of the Z bonds, and are generally of interchangeable properties.
  • the required diazotized monoazo dye can be obtained by tetrazotizing the heterocyclic diamine ##STR13## in a manner which is in itself known and coupling the product, on one side, with the coupling component A 1 --H at pH values of 3 to 12, preferably 4 to 9 and at temperatures of -10° to +30° C.
  • a further particular embodiment of this process for the manufacture of water-soluble diazo dyes of the general formula I consists in coupling a diazotized monoazo dye of the formula XVII ##STR14## wherein Z, y.sup. ⁇ , R 1 , R 2 and n have the above-mentioned meanings, with the second coupling component at pH values between 7 and 14, preferably 7.5 to 10, if the second coupling component is of the aniline or naphthylamine series, at pH values between 0 and 14, preferably 1 and 10, and at temperatures between -10° and +30° C., preferably 0° and 10° C.
  • the required diazotized monoazo dye XVII can be manufactured by coupling the tetrazotized heterocyclic diamine XVI on one side with coupling components VII, VIII or IX at pH values of 7 to 14, preferably 7.5 to 10, and at temperatures of -10° to +30° C.
  • Water-soluble disazo dyes of the general formula I wherein A is a key component III are manufactured by coupling a diazotized monoazo dye of the formula
  • the required diazotized monoazo dye can be manufactured as indicated above.
  • a variant of this process for the manufacture of water-soluble disazo dyes of the general formula I wherein A is a key component III consists in coupling a diazotized monoazo dye
  • the second coupling component A 1 --H in the pH range from 2 to 14, preferably 3 to 10, or, if the remaining coupling component is of the aniline or naphthylamine series, at pH values between 0 and 14, preferably 1 and 10, at temperatures of -10° to +50° C., preferably 0° to +20° C.
  • required for this process variant can be manufactured by tetrazotizing the heterocyclic diamine XVI ##STR15## and coupling on one side, at pH values of 0 to 6, preferably 1 to 4, and at temperatures of -10° to +80° C., preferably 0° to +50° C., with the key coupling component of the formula VII or VIII in a position adjacent to the amino group of the amino-naphthol coupling components.
  • the tetrazotization and all coupling reactions are preferably carried out in an aqueous medium.
  • Water-miscible organic solvents for example alcohols such as methanol or ethanol, can, if appropriate, be present in the aqueous medium.
  • the coupling reactions mentioned can be carried out in the presence of coupling accelerators, for example the known pyridine, urea or thiourea accelerators.
  • coupling accelerators for example the known pyridine, urea or thiourea accelerators.
  • heterocyclic diamines XVI which are suitable for the manufacture of the disazo dyes of the present invention are: 2-(4'-aminophenyl)-5-(or 6)-amino-benzimidazole, 1-methyl-2-(4'-aminophenyl)-6-amino-benzimidazole, 1-methyl-2-(4'-aminophenyl)-5-aminobenzimidazole, 1-ethyl-2-(4'-aminophenyl)-5-amino-benzimidazole, 1-propyl-2-(4'-aminophenyl)-5-amino-benzimidazole, 1-butyl-2-(4'-aminophenyl)-5-amino-benzimidazole, 1-phenyl-2-(4'-aminophenyl)-5-amino-benzimidazole, 1-benzyl-2-(4'-aminophenyl)-5-amino-benzimidazole
  • heterocyclic diamines can be obtained in accordance with the manufacturing methods described in German Offenlegungsschrift No. 2,424,462, pages 13 to 19 and in its U.S. counterpart application Ser. No. 579,156, filed May 20, 1975 (U.S. Pat. No. 4,033,945 granted July 5, 1977).
  • key coupling components are: 2-acetylamino-8-hydroxynaphthalene-6-sulphonic acid, 2-carboxymethylamino-8-hydroxynaphthalene-6-sulphonic acid, 2-benzoylamino-8-hydroxynaphthalene-6-sulphonic acid, 2-methylamino-8-hydroxynaphthalene-6-sulphonic acid, 2-dimethylamino-8-hydroxynaphthalene-6-sulphonic acid, 2-ethylamino-8-hydroxynaphthalene-6-sulphonic acid, 2-phenylamino-8-hydroxynaphthalene-6-sulphonic acid, 3-carboxymethylamino-8-hydroxynaphthalene-6-sulphonic acid, 3-acetylamino-8-hydroxynaphthalene-6-sulphonic acid, 3-phenylamino-8-hydroxynaphthalene-6-sulphonic acid, 3-benzoylamino-8-hydroxynaphthalene-6-sulphonic acid, 1-acetylamino
  • non-key coupling components suitable for the manufacture of the disazo dyes according to the present invention are: phenol, 2-methylphenol, 4-methylphenol, 3-chlorophenol, 3-methoxyphenol, 2-hydroxybenzenesulfonic acid, 3-hydroxybenzenesulfonic acid, 1,3-dihydroxybenzene, 1.3-dihydroxy-2-chlorobenzene, 1,3-dihydroxy-4-chlorobenzene, 1,3-dihydroxy-5-methylbenzene, 1,3-dihydroxy-4-hexylbenzene, 1,3-dihydroxybenzene-5-sulphonic acid, 1-amino-3-hydroxybenzene, 1-amino-3-hydroxy-4-chlorobenzene, 1-(2'-methylphenylamino)-3-hydroxybenzene, 1-(phenylamino)-3-hydroxybenzene, 3-aminophenol-4-sulphonic acid, 3-aminophenol-6-sulphonic acid, 1,3-diaminobenzene, 1,3-d
  • the disazo dyes of the present invention are outstandingly suitable for use as direct dyes for dyeing and printing natural or synthetic fibre material containing hydroxyl groups or containing nitrogen, particularly cotton and regenerated cellulose as well as wool, wool-cotton combinations, silk, polyamide, leather and paper.
  • the dyeing and printing can be carried out by the customary processes.
  • the dyeings are distinguished by good fastness properties, especially by good fastness to wet processing, for example fastness to water, washing at 40° C. and washing at 60° C., and by good fastness to perspiration (alkaline and acid) and fastness to acid.
  • X is ##STR16## and especially ##STR17## the disazo dyestuffs of the present invention are extensively absorbed onto the fibre materials to be dyed when dyeing by the exhaust process, so that a nearly clear residual liquor is obtained.
  • the disazo dyes of the present invention are superior to related prior art dyes including those described in the U.S. Pat. No. 4,033,945.
  • the new dyes are particularly suitable for dyeing fibres composed of cotton and regenerated cellulose and for dyeing polyamide, leather and paper.
  • a yellowish-tinged brown dyeing with good depth of color and with good fastness properties, especially good fastness to washing and fastness to perspiration as well as good stability to acid is obtained.
  • a solution of 36.1 parts of 1-acetylamino-8-hydroxynaphthalene-3,6-disulfonic acid, 4 parts of sodium hydroxide and 20 parts of sodium carbonate in 150 parts of water is then added in the course of approximately 10 minutes to the buffered solution of the tetrazo component, with stirring, and stirring is continued for 10 minutes at 0°-5° C. and at a pH of 7.5 to 8.5.
  • a solution of 31.5 parts of 2-phenylamino-8-hydroxynaphthalene-6-sulfonic acid, 4 parts of sodium hydroxide and 20 parts of sodium carbonate in 200 parts of water is then added rapidly to the coupling mixture.
  • column 1 the key coupling component IIa or IIIa used.
  • column 4 the colour shade produced on cotton by dyeing in accordance with the example.
  • the pH of the suspension of the diazotised monoazo dyestuff is then adjusted to 3 with 30% aqueous hydrochloric acid and 20 parts of sodium acetate are added.
  • a neutral solution of 31.1 parts of 2-hydroxyethylamino-8-hydroxynaphthalene-6-sulfonic acid in 150 parts of water is then run in in the course of 1 hour. Stirring is continued for approximately 12 hours at pH 4-5 and at 40 to 50° C. in order to complete the acid coupling reaction.
  • the red disazo dye of the structure ##STR27## is filtered off and dried at 60°-70° C.
  • a solution of 36.1 parts of 1-acetylamino-8-hydroxynaphthalene-3.6-disulfonic acid, 4 parts of sodium hydroxide and 40 parts of sodium carbonate in 150 parts of water is then added to the suspension of the diazotised monoazo dyestuff.
  • substitution of sulfo groups or hydrocarbon groups or carboxy groups or chlorine anywhere in the final dye molecule does not significantly affect its dyeing characteristics.
  • the substitution of sulfo groups or carboxy groups, particularly the former, is helpful in that this improves the water-solubility of the final dye. More than four such water-solubilizing groups in one dye molecule may have an adverse influence.
  • the dyes of the present invention will in use often have these groups partially or completely in salt form as a result of neutralization with sodium, potassium or ammonium compounds or the like that may be present in the reaction mixtures in which they are formed or in the dye mixtures in which they are applied to the materials to be dyed.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Coloring (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
US05/778,049 1976-03-24 1977-03-16 Water-soluble disazo dyestuffs containing a 2-phenyl-benzimidazolyl,-benzoxazolyl or-benzthiazolyl middle component Expired - Lifetime US4143033A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE2612454 1976-03-24
DE19762612454 DE2612454A1 (de) 1976-03-24 1976-03-24 Wasserloesliche disazofarbstoffe, ihre herstellung und verwendung

Publications (1)

Publication Number Publication Date
US4143033A true US4143033A (en) 1979-03-06

Family

ID=5973300

Family Applications (1)

Application Number Title Priority Date Filing Date
US05/778,049 Expired - Lifetime US4143033A (en) 1976-03-24 1977-03-16 Water-soluble disazo dyestuffs containing a 2-phenyl-benzimidazolyl,-benzoxazolyl or-benzthiazolyl middle component

Country Status (12)

Country Link
US (1) US4143033A (enrdf_load_stackoverflow)
JP (1) JPS52117324A (enrdf_load_stackoverflow)
BE (1) BE852809A (enrdf_load_stackoverflow)
BR (1) BR7701773A (enrdf_load_stackoverflow)
CA (1) CA1075232A (enrdf_load_stackoverflow)
CH (1) CH618996A5 (enrdf_load_stackoverflow)
DE (1) DE2612454A1 (enrdf_load_stackoverflow)
FR (1) FR2357612A1 (enrdf_load_stackoverflow)
GB (1) GB1545347A (enrdf_load_stackoverflow)
IN (1) IN146137B (enrdf_load_stackoverflow)
IT (1) IT1115282B (enrdf_load_stackoverflow)
NL (1) NL7703006A (enrdf_load_stackoverflow)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2700805A1 (de) * 1977-01-11 1978-07-20 Cassella Farbwerke Mainkur Ag Wasserloesliche disazofarbstoffe, ihre herstellung und verwendung

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2151470A1 (de) * 1971-10-15 1973-04-19 Bayer Ag Polyazofarbstoffe
US4033945A (en) * 1974-05-20 1977-07-05 Cassella Farbwerke Mainkur Aktiengesellschaft Water-soluble trisazo 8-amino-naphthol-1 dyes

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2151470A1 (de) * 1971-10-15 1973-04-19 Bayer Ag Polyazofarbstoffe
US4033945A (en) * 1974-05-20 1977-07-05 Cassella Farbwerke Mainkur Aktiengesellschaft Water-soluble trisazo 8-amino-naphthol-1 dyes

Also Published As

Publication number Publication date
BR7701773A (pt) 1978-01-17
NL7703006A (nl) 1977-09-27
FR2357612B1 (enrdf_load_stackoverflow) 1980-12-12
CA1075232A (en) 1980-04-08
DE2612454A1 (de) 1977-10-06
CH618996A5 (enrdf_load_stackoverflow) 1980-08-29
IT1115282B (it) 1986-02-03
JPS52117324A (en) 1977-10-01
GB1545347A (en) 1979-05-10
BE852809A (fr) 1977-09-23
FR2357612A1 (fr) 1978-02-03
IN146137B (enrdf_load_stackoverflow) 1979-03-03

Similar Documents

Publication Publication Date Title
US4033945A (en) Water-soluble trisazo 8-amino-naphthol-1 dyes
US3346553A (en) Azo-dyestuffs containing aminoalkyl-enesulfonylamino groups
DE1089095B (de) Verfahren zur Herstellung von Farbstoffen
US4143033A (en) Water-soluble disazo dyestuffs containing a 2-phenyl-benzimidazolyl,-benzoxazolyl or-benzthiazolyl middle component
US4144231A (en) Soluble trisazo dyestuffs containing a 2-phenyl-benzimidazolyl, -benzoxazolyl or -benzthiazolyl middle component
US2446662A (en) Chromium complexes of pyrazolone azo dyes
US2232870A (en) Azo dyestuffs
US2164785A (en) Azo dyes
US3197456A (en) Azo-dyestuffs
US2404198A (en) Disazo and polyazo benzidine type dyestuffs
US4560744A (en) Azo dye 2:1-chromium complexes
US4225492A (en) Water-soluble disazo dyestuffs, prepared from unsymmetrical heterocyclic diamines
US3222354A (en) Water-soluble reactive azo dyes
US2690438A (en) Azo-dyestuffs
US2040368A (en) Azo-dyestuffs containing chromium and process of preparing them
US2750375A (en) Polyazo-dyestuffs
US4973672A (en) Water-soluble aminonaphthol disazo dyestuffs, their preparation and their use
US4137228A (en) Water-soluble, copper containing trisazo compounds having a 2-(4&#39;phenylene)-benzimidazoyl-(5 or 6),-benzoxazolyl-(5), or -benzthiazolyl-(5) component
US2405353A (en) Polyazo dyestuffs of the stilbene series and process of making same
US2769805A (en) Metalliferous trisazo-dyestuffs
US2779756A (en) Metalliferous trisazo dyestuffs
US3260713A (en) Water-soluble monoazo-dyestuffs
US2693464A (en) Triazole azo and azoxy dyestuffs
US2095484A (en) Azodyestuffs
US3109840A (en) I-soanha